Stabilized high film strength



@ntented 9. 1i

OFFICE s'rsnmznn man mm s'rnmworn LUBRICATING oms Bert H. P and Waldo L.Steiner, Ponca (lity,

Okla assignors to Continental Oil moms.

Ponca City, Oklai, a corporation or Delaware No Drawing.

4 Claims.

7 our invention relates to a stabilized hish mm t r w. lubricating oil,and more particularly to a. omposition oi matter comprising ahydrocarhon oil of inc iilm strength obtained by the 7 addition of achlorinated organic compound, which composition has been stabilized. I

This application is a continuation-in-part of our co-pendingapplication, serial No. 64,706, filed February 19, 1936, Patent No.2,217,173, issued October 8, 1990.

It is known that the addition of small quantitles of chlorinated organiccompounds in general to a by oil will impart thereto an increased filmstrength. As ordinarily prepared, the chlorinated carbon compounds arerefined after chlorination by blowing with air to remove to economicallyrefine a chlorinated compound as v for example, a. chlorinated ester ofa fatty acid, this treating should not be too severe. Therefore, thefinished product is never as stable as is desired especially ii it is tobe stored in iron contsiners during the warm months of the year. What istrue oi the chloro-ester is true broadly for all chlorinated organiccompounds in general. We find that chlorinated compounds and esters inparticular, stored under these conditions, quite often develophydrochloric acid in a few weeks time. When this occurs the productturns dark and some of the esters hydrolize, thereby increasing the freefatty acid. This is obviously objectionable.

n ples of the ordinarily prepared and ed chloro-esters are to sunlight,either directly or indirectly, for a few days in glass containers, somehydrochloric acid develops and tends to cause hydrolysis. This isanalogous to the development oi hydrochloric acid in the derh in ironcon i: ers d the warm months test was developed to consists thestability 50 oi the chloro-esters in sunlight and the stability in ironcontainers. Standard one-pound crease were cleaned 25 cc. oi thechloro-esters tobet weropouredintcthem. Thecans were men held st sec d.until they developed 55 Application February 24 1940, sci-1n No. szoazo(Cl. ass-54) hydrochloric acidand turned dark. .It was found that 1%hours without change at 240 F. in this test was equivalent to aboutthree weeks exposure to indirect sunlight.

We have found that a number of compounds,

when added to. halogenated organic compounds in small amounts, greatlyincreased the period of time which was required to induce the formationof hydrochloric acid under the conditions of 10 these two tests. Thecompounds which had the greatest efiect were the terpene hydrocarbons.In particular, pinene was found to be an extremely potent stabilizer.straight methyl chloro stearate developed a strong 16 odor ofhydrochloric acid in less than a month's time. A blend of one per centof pinene in the same chloro-ester did not develop a trace oihydrochloric acid after a year's exposure. The length of time beforewhich hydrochloric acid-de- 20 veloped in the iron can test at 240 F.described above, was increased by 900 per cent by the addition of oneper cent of pinene.

Other terpene hydrocarbons which can be em.- ployed are myrcene,ocimene, limonene, hemi- 2 terpenes, di-terpenes, polyterpenes and thelike.

Terpene derivatives are also of value although they are not as eiiectiveas the hydrocarbons. Examples of these are geraniol, citronellol,cineol, carvine, citrol, and the like.

A second class of compounds which we have discovered very eflective asstabilizers for halogenated compounds is the hydrogenated derivatlves ofnaphthalene, di-, tetra-, hexa-, octo-, and deca-hydronaphthalene. Forexample, one per cent of tetra-hydronaphthalene improved the stabilityof methyl chloro stearate 800 per cent in the test where the sampleswere exposed to sunlight.

A third class or compounds which has considerable stabilizing influenceson halogenated compounds are the hydroxy aromatic compounds. one percent of phenol, para-cresol, naphthol, andpara-hydroxy diphenyl eachincreased the stability of the chloro esters by 500 to 900 per 5 cent.Derivatives of the phenols are also operative. One per cent of orthonitro phenol increased the stability of methyl chloro stearate by 800per cent.

While a number of other compounds have some stabilizing influence onchloro-esters, the above three groups are outstanding. Three compoundsnot included in these groups, which have considerable merit, arecholesterol, ethyl abietate, and acetal. Compounds which react withhydrochloric acid easily and hold the halogen acid For example, the

firmly have been found. to be of advantage in practicing our invention.Some of the other halogenated organic compounds which have beenstabilized by the previously mentioned stabilizing agents are:

Halogenated aliphatic hydrocarbons such as halogenated wax andhalogenated petroleum oils; halogenated aromatic hydrocarbons such ashalogenated benzene, naphthylene, diphenyl, anthracene, and the like;halogenated aliphatic, ar-

omatic, and heterocyclic alcohols,- aldehydes,

chloro ester gives a lubricating oil blend oi improved s a i The sterolsbroadly-are or valu in our invention. Cholesterol, a compound irom thisclass has been previously mentioned herein as a representative oi theclass of polycyclic ring alcohols I "with hydrocarbon substituents onthe ring. The

primary, secondary, and tertia y P yclic ring alcohols with one or moreside chains are useketones, acids, esters, ether s, etc.; mixtures '01various halogenated organic compounds with each other and with amines,nitro compounds. phosphorus containing compounds, thio compounds, etc. V

In practicing this invention, quantities of the stabilizer of as smallas .01 per cent of the ml in this invention. Some oi the compoundsincluded underthe term sterols are chemically saturated and others arechemicallv unsatm'ated. For example, the substituent group may be anisoamyl group or a, vinyl group. The sterols belong to the class ofpolyterpenes and are intimately related to they bile acids.

chlorinated carbon compound content maybe used with some good eiiects.The more or the stabilizer used with the chloro-ester, the more stablethe resulting blend will be, however, the near maximum effect isobtained with one per cent or less. For example, .1 per cent of pineneincreased the stability in the iron can test 100 per-cent, while .25 percent increased the stability 500 per cent and one per cent increased thestability only 900 per cent.

si veness of blends oi halogenated organic compounds in lubricating oil.For example, a blend of one per cent of fairly stable methyl chlorostearate in oil caused a loss of mg. per 100 sq. cm. of bearing metal ina corrosion test conducted at 300 F. for forty-eight hours. A blend ofone, per cent of the same ester stabilized with one per cent of pinenein oil in the same test caused a loss or 8 mg. per 100 sq. cm. of thesame bearing material. Therefore, the stabilizer in the iromrape oil andclionasterol may be The sterols as mentioned herein contain an al- Thebest known representatives of the stem]: are choleateroL'isocholesterol, phytosterol, B cholestanol, coprosterol, chortosterol,and bombicesterol. Other sterols such as brassicasterol mentioned.

cohol or (OH) group but diiier from the alcohols oi the aliphatic seriesin that they are not converted into fatty acids having the same numberof carbon atoms by heating with potash lime or soda lime.

Having thus described our invention, we claim:

1. A composition or matter comprising in combination a major portion ora hydrocarbon oil, from b to 10% by weight of a chlorinated carboncompound. and from .00i% to 2% by weight of a sterol.

2. A composition of matter comprising in combination a major portion ora hydrocarbon oil,

from /2 to 10% by weight of a chlorinated carbon compound, and irom.001% to 2% by weight of cholesterol.

3. A composition of matter comprising in combination a major portion ofa. hydrocarbon oil, from /2 to 10% by weight oi' a chlorinated carboncompound, and from .00i% to 2% by weight 01 isocholesterol.

4. A composition of matter comprising in combination a major portion ofa hydrocarbon oil, from V to 10% by weight of a chlorinated carboncompound, and from .001% to 2% by weight 01' 'phytosterol.

BERT H. LINCOLN. WALDO L. STEINER.

